CN105924644B - Polyarylsulfone and preparation method thereof - Google Patents

Polyarylsulfone and preparation method thereof Download PDF

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CN105924644B
CN105924644B CN201610301038.1A CN201610301038A CN105924644B CN 105924644 B CN105924644 B CN 105924644B CN 201610301038 A CN201610301038 A CN 201610301038A CN 105924644 B CN105924644 B CN 105924644B
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polyarylsulfone
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周光远
王红华
王志鹏
杨玉
张兴迪
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Jilin Zhongke polymerization Engineering Plastics Co., Ltd.
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0666—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0677—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
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Abstract

The polyarylsulfone provided by the invention has a structure shown in a formula (I) or a formula (II), wherein the structure shown in the formula (I) or the structure shown in the formula (II) has a structure shown in Ar, so that the prepared polyarylsulfone has high glass transition temperature (Tg can reach 365 ℃), can be dissolved in halogenated alkanes such as chloroform and dichloromethane and aprotic solvents such as NMP at room temperature, and can be dissolved in aprotic polar solvents such as DMF and DMAc after being heated. Further, the polyarylsulfone obtained by the invention has good processing performance. In addition, the preparation method provided by the invention is simple, the raw material source is wide, and the industrial production can be realized.

Description

Polyarylsulfone and preparation method thereof
Technical Field
The invention relates to the field of polymers, in particular to polyarylsulfone and a preparation method thereof.
Background
The polyarylsulfone is a novel amorphous aromatic high-temperature resistant resin, has the advantages of high heat-resistant grade, excellent mechanical property, electrical property and radiation resistance, fatigue resistance, flame retardance, impact resistance, creep resistance and the like, is particularly suitable for being used as a high-performance composite resin matrix and super engineering plastics, has wide application in a plurality of high and new technical fields such as space navigation, electronic information, energy and the like, and becomes a great hotspot in the research field of high polymer materials.
In recent years, with the further development of high and new technologies, the requirements for polyarylsulfone materials are higher and higher, and the development of novel polyarylsulfone and polyarylsulfone resins with higher heat resistance grade and more convenient processing through chemical and physical modification researches is a very active topic. The prior polyarylsulfone with more applications mainly comprises Udel, Radel and the like, Tg(glass transition temperature) is 185 ℃ and 220 ℃, the long-term use temperature can reach 150 ℃ and 190 ℃, and when the temperature exceeds TgLater, the performance of the material degrades very quickly.
McGill University reports on ACS Macro Lett a polyarylsulfone polymer containing benzimidazolone, which has a glass transition temperature of 348 ℃, is soluble in NMP and partially soluble in chloroform,
the polymer structure is shown below:
Figure BDA0000984912890000011
the introduction of imidazole can greatly increase the Tg of the polymer and improve the heat resistance of the polymer. The monomer is applied to a preparation formula of polyaryletherketone, for example, Chinese patent ZL 201310440208.0 discloses aromatic polyketone containing an imidazole structure, Tg can reach 326 ℃, but polymer solubility is poor. The structural formula of the polymer is
Figure BDA0000984912890000021
Wherein X is an oxygen or sulfur atom.
Chinese patent ZL 201310440106.0 also discloses polyaryletherketone copolymer containing imidazole structure, the glass transition temperature of the modified polyaryletherketone can be as high as 270 ℃, the 5% thermal weight loss temperature can be as high as 541 ℃, and the carbon residue rate at 600 ℃ can be 70.7%. By introducing a new structure, the solubility of the polymer can be improved, so that the polymer has better solubility in halogenated hydrocarbons such as 1, 1-dichloroethane, 1, 2-trichloroethane and the like, DMF, DMAc and NMP. The copolymer has the structural formula:
Figure BDA0000984912890000022
at present, the processing difficulty of the polymer material is often reduced by dissolving the polymer material in a solvent, but the solubility of the polyarylsulfone is not good. Therefore, it is a technical problem to be solved to obtain a polyarylsulfone having not only good solubility but also good heat resistance.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a polyarylsulfone and a preparation method thereof, wherein the polyarylsulfone provided by the present invention has good solubility in a solvent and a high glass transition temperature.
The invention provides polyarylsulfone with a structure shown in a formula (I) or a structure shown in a formula (II),
Figure BDA0000984912890000031
ar is formula (Ar-1) or formula (Ar-2);
Figure BDA0000984912890000032
wherein A is1And A2Independently selected from S or O;
the R is1And R2Independently selected from H, NH2、NO2Or C1-C5 alkyl, and R1And R2Not H at the same time;
the R is3And R4Independently selected from aryl of H, C6-C50 or substituted aryl of C6-C50;
the Ar ' is from a third monomer H-Ar ' -H, and the H-Ar ' -H is selected from an aromatic compound with two active functional groups or an aromatic heterocyclic compound with two active functional groups;
n is an integer more than or equal to 2;
and m is an integer more than or equal to 2.
Preferably, said R is3Selected from H, phenyl and 4-fluorophenyl, 4-chlorophenyl, 4-aminophenyl or 4-nitrophenyl.
Preferably, said R is4Selected from H, phenyl and 4-fluorophenyl, 4-chlorophenyl, 4-aminophenyl or 4-nitrophenyl.
Preferably, the reactive functional group in the aromatic compound having two reactive functional groups is a phenolic hydroxyl group or an amine group;
the active functional group in the aromatic heterocyclic compound with two active functional groups is a phenolic hydroxyl group or an amine group.
Preferably, the H-Ar ' -H is selected from the group consisting of H-Ar-H, hydroquinone, 4' -dihydroxybiphenyl, 4' -dihydroxybenzophenone, 4' -dihydroxydiphenylsulfone, 4' -dihydroxydiphenylether, 4' -dihydroxybiphenyl sulfide, 2-bis (4-hydroxyphenyl) propane, 4' - (hexafluoroisopropylidene) bisphenol, 4' - (1, 4-phenylenediisopropyl) diphenol, 3-bis (4-hydroxyphenyl) -1(3H) -isobenzofuranone, 3' -bis (4-hydroxyphenyl) phthalimidine, 6- (2-hydroxyphenyl) -piperazin-3- (6H) -one, and mixtures thereof, 6- (4-hydroxyphenyl) -piperazin-3- (6H) -one, 4- (4-hydroxyphenyl) -2, 3-phthalazinone, 2-hydroxycarbazole, 3-hydroxycarbazole, 9-bis (4-hydroxyphenyl) fluorene, 6, 13-bistripterene diol, 2, 5-triptterene diol, 5 '-bis (2-4- (hydroxyphenyl) -benzimidazole) or 2, 6-bis (4-hydroxyphenoxy) -4' - (2,3,4,5, 6-pentaphenylphenyl) benzophenone.
The invention also provides a preparation method of the polyarylsulfone shown in the formula (I), which comprises the following steps:
mixing H-Ar-H, a compound of a formula (III), a catalyst, a water-carrying agent and a solvent for reaction to obtain polyarylsulfone shown in a formula (I),
ar in the H-Ar-H is a formula (Ar-1) or a formula (Ar-2);
Figure BDA0000984912890000041
wherein A is1And A2Independently selected from S or O;
the R is1And R2Independently selected from H, NH2、NO2Or C1-C5 alkyl, and R1And R2Not H at the same time;
the R is3And R4Independently selected from aryl of H, C6-C50 or substituted aryl of C6-C50;
Figure BDA0000984912890000042
wherein X is halogen or NO2。
Preferably, the solvent is one or more of N-methylpyrrolidone, N-cyclohexylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, sulfolane, dimethylimidazolone and diphenylsulfone.
Preferably, the catalyst is carbonate, preferably one or more of potassium carbonate, sodium bicarbonate and calcium carbonate.
The invention also provides a preparation method of the polyarylsulfone shown in the formula (II), which comprises the following steps:
mixing H-Ar-H, a compound of a formula (III), H-Ar' -H, a catalyst, a water-carrying agent and a solvent for reaction to obtain polyarylsulfone shown in a formula (I),
ar in the H-Ar-H is a formula (Ar-1) or a formula (Ar-2);
Figure BDA0000984912890000051
wherein A is1And A2Independently selected from S or O;
the R is1And R2Independently selected from H, NH2、NO2Or C1-C5 alkyl, and R1And R2Not H at the same time;
the R is3And R4Independently selected from aryl of H, C6-C50 or substituted aryl of C6-C50;
Figure BDA0000984912890000052
wherein X is halogen or NO2；
The H-Ar' -H is selected from aromatic compounds with two active functional groups or aromatic heterocyclic compounds with two active functional groups.
Preferably, the first aprotic solvent is added in an amount such that the solid content is 8 to 40 wt%.
Compared with the prior art, the polyarylsulfone provided by the invention has a structure shown as a formula (I) or a structure shown as a formula (II), wherein the structure shown as Ar is formed in the structure shown as the formula (I) or the structure shown as the formula (II), so that the prepared polyarylsulfone has high glass transition temperature and good solubility in a solvent, and the processing performance of the polyarylsulfone obtained by the invention is good. In addition, the preparation method provided by the invention is simple, the raw material source is wide, and the industrial production can be realized.
Drawings
FIG. 1 is a DSC two-time temperature rise graph of the polyarylsulfone of formula (I-a) prepared in example 1 of the present invention;
FIG. 2 is a thermogravimetric analysis chart of the polyarylsulfone represented by the formula (I-a) prepared in example 1 of the present invention.
Detailed Description
The invention provides polyarylsulfone with a structure shown in a formula (I) or a structure shown in a formula (II),
Figure BDA0000984912890000061
ar is formula (Ar-1) or formula (Ar-2);
Figure BDA0000984912890000062
wherein A is1And A2Independently selected from S or O;
the R is1And R2Independently selected from H, NH2、NO2Or C1-C5 alkyl, and R1And R2Not H at the same time;
the R is3And R4Independently selected from aryl of H, C6-C50 or substituted aryl of C6-C50;
the Ar ' is from a third monomer H-Ar ' -H, and the H-Ar ' -H is selected from an aromatic compound with two active functional groups or an aromatic heterocyclic compound with two active functional groups;
n is an integer more than or equal to 2;
and m is an integer more than or equal to 2.
According to the invention, A is1Preferably O, said A2Preferably O.
According to the invention, said R1Preferably H, NH2、NO2Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, n-pentyl, isopentyl or neopentyl, more preferably NH2、NO2Methyl, ethyl or propyl.
According to the invention, said R1Preferably H, NH2、NO2Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, n-pentyl, isopentyl or neopentyl, more preferably NH2、NO2Methyl, ethyl or propyl.
According to the invention, said R2Preferably H, NH2、NO2Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, n-pentyl, isopentyl or neopentyl, more preferably NH2、NO2Methyl, ethyl or propyl. Wherein, R is1And R2Not H at the same time.
According to the invention, said R3Preferably H, C10-C30 aryl or C10-C30 substituted aryl, more preferably H, C15-C20 aryl or C15-C20 substituted aryl; more specifically, said R3Selected from H, phenyl and 4-fluorophenyl, 4-chlorophenyl, 4-aminophenyl or 4-nitrophenyl.
According to the invention, said R4Preferably H, C10-C30 aryl or C10-C30 substituted aryl, more preferably H, C15-C20 aryl or C15-C20 substituted aryl; more specifically, said R4Selected from H, phenyl and 4-fluorophenyl, 4-chlorophenyl, 4-aminophenyl or 4-nitrophenyl. Wherein, R is3And R4Preferably not both.
According to the invention, said Ar ' is derived from a third monomer H-Ar ' -H, said H-Ar ' -H being selected from aromatic compounds having two reactive functional groups or aromatic heterocyclic compounds having two reactive functional groups; wherein the carbon number of the aromatic compound is preferably 6 to 80, more preferably 10 to 60, most preferably 15 to 50, most preferably 30 to 40; the carbon number of the aromatic heterocyclic compound is preferably 5-80, more preferably 10-60, most preferably 15-50, and most preferably 30-40; the active functional groups are phenolic hydroxyl groups or amine groups, and the two active functional groups in the compound can be the same functional group or different functional groups; more specifically, the H-Ar ' -H is selected from the group consisting of H-Ar-H, hydroquinone, 4' -dihydroxybiphenyl, 4' -dihydroxybenzophenone, 4' -dihydroxybiphenyl sulfone, 4' -dihydroxydiphenyl ether, 4' -dihydroxybenzophenone sulfide, 2-bis (4-hydroxyphenyl) propane, 4' - (hexafluoroisopropylidene) bisphenol, 4' - (1, 4-phenylenediisopropyl) diphenol, 3-bis (4-hydroxyphenyl) -1(3H) -isobenzofuranone, 3' -bis (4-hydroxyphenyl) phthalimidine, 6- (2-hydroxyphenyl) -piperazin-3- (6H) -one, and, 6- (4-hydroxyphenyl) -piperazin-3- (6H) -one, 4- (4-hydroxyphenyl) -2, 3-phthalazinone, 2-hydroxycarbazole, 3-hydroxycarbazole, 9-bis (4-hydroxyphenyl) fluorene, 6, 13-bistripterene diol, 2, 5-triptterene diol, 5 '-bis (2-4- (hydroxyphenyl) -benzimidazole) or 2, 6-bis (4-hydroxyphenoxy) -4' - (2,3,4,5, 6-pentaphenylphenyl) benzophenone.
According to the invention, n is preferably an integer of 2 or more, more preferably 3. ltoreq. n.ltoreq.200, most preferably 5. ltoreq. n.ltoreq.100, most preferably 10. ltoreq. n.ltoreq.50; m is preferably an integer of 2 or more, more preferably 3. ltoreq. m.ltoreq.200, most preferably 5. ltoreq. m.ltoreq.100, most preferably 10. ltoreq. m.ltoreq.50.
More specifically, the polyarylsulfone is of formula (I-a), formula (I-b), formula (I-c), formula (I-d), formula (II-a), formula (II-b) or formula (II-c).
Figure BDA0000984912890000081
Wherein n is an integer not less than 2, and m is an integer not less than 2.
The polyarylsulfone provided by the invention has a structure shown in a formula (I) or a formula (II), wherein the structure shown in the formula (I) or the structure shown in the formula (II) has a structure shown in Ar, so that the prepared polyarylsulfone has high glass transition temperature and good solubility in a solvent, and the processing performance of the polyarylsulfone obtained by the invention is improved.
The invention also provides a preparation method of the polyarylsulfone shown in the formula (I), which comprises the following steps:
mixing H-Ar-H, a compound of formula (III), a water-carrying agent, a catalyst and a solvent for reaction to obtain polyarylsulfone shown in formula (I),
ar in the H-Ar-H is a formula (Ar-1) or a formula (Ar-2);
Figure BDA0000984912890000091
wherein A is1And A2Independently selected from S or O;
the R is1And R2Independently selected from H, NH2、NO2Or C1-C5 alkyl, and R1And R2Not H at the same time;
the R is3And R4Independently selected from aryl of H, C6-C50 or substituted aryl of C6-C50;
Figure BDA0000984912890000092
wherein X is halogen or NO2。
According to the invention, in said H-Ar-H, A1、A2、R1、R2、R3And R4The selection range of (B) is the same as the selection range of the substituent group in the polyarylsulfone shown in the formula (I); in the formula (III), X is preferably F, Cl, Br or NO2(ii) a The solvent is preferably an aprotic solvent, and particularly preferably one or more of N-methylpyrrolidone, N-cyclohexylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, sulfolane, dimethylimidazolone and diphenyl sulfone; the catalyst is preferably carbonate, and more preferably one or two of calcium carbonate and potassium carbonate; the invention also has no special requirements for the source of each raw material, and the raw materials can be directly purchased or self-made by the technicians in the field. The molar ratio of H-Ar-H to the compound of formula (III) is preferably 1: (1-1.01); the molar ratio of H-Ar-H to carbonate is preferably 1: (1-5), more preferably 1: (1-3), most preferably 1: (1-2); the amount of the solvent added is preferably such that the solid content of the reaction system is from 8 wt% to 40 wt%, more preferably from 15 wt% to 35 wt%, most preferably from 18 wt% to 30 wt%.
In order to better perform the reaction, the invention preferably mixes H-Ar-H, the compound shown in the formula (III), the water-carrying agent, the catalyst and the solvent for azeotropic removal of water to obtain a water-removed mixed solution; then heating the dehydrated mixed solution for reaction to obtain polyarylsulfone; the water-carrying agent is preferably toluene, the water removing temperature is preferably 110-130 ℃, and the water removing time is preferably 2-4 hours; the heating reaction temperature is preferably 130-300 ℃, more preferably 150-250 ℃, and most preferably 190-220 ℃.
In order to make the obtained polyarylsulfone more pure, the polyarylsulfone obtained after heating reaction is preferably diluted by a solvent, and then a precipitator is added for precipitation to obtain the purified sulfone compound. Wherein, the solvent is preferably one or more of N-methylpyrrolidone, N-cyclohexylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, sulfolane, dimethylimidazolone and diphenylsulfone, which can be the same or different from the solvent for reaction, and is not particularly limited; the addition amount of the solvent is preferably 5-10% of the solid content of the reaction system, and more preferably 8-10%; the precipitant is a precipitant well known to those skilled in the art, and is not particularly limited, and in the present invention, one or more of water, ethanol, acetic acid, and hydrochloric acid are preferred, and a mixed solution of three is more preferred.
The invention also provides a preparation method of the polyarylsulfone shown in the formula (II), which comprises the following steps:
mixing H-Ar-H, a compound of a formula (III), H-Ar' -H, a water-carrying agent, a catalyst and a solvent for reaction to obtain polyarylsulfone shown in a formula (I),
ar in the H-Ar-H is a formula (Ar-1) or a formula (Ar-2);
Figure BDA0000984912890000101
wherein A is1And A2Independently selected from S or O;
the R is1And R2Independently selected from H, NH2、NO2Or C1-C5 alkyl, and R1And R2Not H at the same time;
the R is3And R4Independently selected from H, C6-C50Aryl of (a) or substituted aryl of C6 to C50;
Figure BDA0000984912890000102
wherein X is halogen or NO2；
The H-Ar' -H is selected from aromatic compounds with two active functional groups or aromatic heterocyclic compounds with two active functional groups.
According to the invention, in said H-Ar-H, A1、A2、R1、R2、R3And R4The selection range of (B) is the same as the selection range of the substituent group in the polyarylsulfone shown in the formula (I); in the formula (III), X is preferably F, Cl, Br or NO2(ii) a Ar 'in the H-Ar' -H is selected to be the same as that in the polyarylsulfone shown in the formula (II); the solvent is preferably an aprotic solvent, and particularly preferably one or more of N-methylpyrrolidone, N-cyclohexylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, sulfolane, dimethylimidazolone and diphenyl sulfone; the catalyst is preferably carbonate, more preferably one or more of potassium carbonate, sodium bicarbonate and calcium carbonate, and most preferably one or two of calcium carbonate and potassium carbonate; the invention also has no special requirements for the source of each raw material, and the raw materials can be directly purchased or self-made by the technicians in the field. The molar ratio of H-Ar-H to the compound of formula (III) is preferably 1: (1-1.01); the molar ratio of H-Ar-H to the compound of formula (III) is preferably 1: (1-1.01); the molar ratio of H-Ar' -H to carbonate is preferably 1: (1-5), more preferably 1: (1-3), most preferably 1: (1-2); the amount of the solvent added is preferably such that the solid content of the reaction system is from 8 wt% to 40 wt%, more preferably from 15 wt% to 35 wt%, most preferably from 18 wt% to 30 wt%.
In order to better perform the reaction, the invention preferably mixes H-Ar-H, the compound of formula (III), H-Ar' -H, the water-carrying agent, the catalyst and the solvent, azeotropy removes water to obtain a mixture after removing water; then heating the dehydrated mixed solution for reaction to obtain polyarylsulfone; the water-carrying agent is preferably toluene, the water removing temperature is preferably 110-130 ℃, and the water removing time is preferably 2-4 hours; the heating reaction temperature is preferably 130-300 ℃, more preferably 150-250 ℃, and most preferably 190-220 ℃.
In order to make the obtained polyarylsulfone more pure, the polyarylsulfone obtained after heating reaction is preferably diluted by a solvent, and then a precipitator is added for precipitation to obtain the purified sulfone compound. Wherein, the solvent is preferably one or more of N-methylpyrrolidone, N-cyclohexylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, sulfolane, dimethylimidazolone and diphenylsulfone, which can be the same or different from the solvent for reaction, and is not particularly limited; the addition amount of the solvent is preferably 5-10 wt% of the solid content of the reaction system, and more preferably 8-10 wt%; the precipitant is a precipitant well known to those skilled in the art, and is not particularly limited, and in the present invention, one or more of water, ethanol, acetic acid, and hydrochloric acid are preferred, and a mixed solution of three is more preferred.
The preparation method of the polyarylsulfone provided by the invention is obtained by mixing and reacting H-Ar-H, the compound of the formula (III), a catalyst and a solvent, or mixing and reacting H-Ar-H, the compound of the formula (III), H-Ar' -H, the catalyst and the solvent, and has the advantages of simplicity, wide raw material source and low cost, and the obtained polymer not only has high glass transition temperature, but also has good dissolubility in the solvent; has wide industrial application prospect.
The following will clearly and completely describe the technical solutions of the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Sequentially adding 1.622g (0.01mol) of dimethyl benzimidazolone (DmHBI), 2.543g (0.01mol) of difluoro diphenyl sulfone (DFS), 2.763g of potassium carbonate, 20g of sulfolane and 20ml of toluene into a 100ml three-neck round-bottom flask, heating to 130 ℃ for azeotropic dehydration, keeping the temperature for 2h, heating to remove the toluene, continuously heating to 210 ℃, reacting for 5h, cooling, adding 20ml of dimethyl acetamide for dilution, precipitating in a mixed solution of ethanol, water and acetic acid, filtering precipitates, extracting with deionized water in a Soxhlet extractor for 12h, removing inorganic salts and a reaction solvent, drying to obtain the polyarylsulfone shown in the formula (I-a),
the reaction formula is as follows:
Figure BDA0000984912890000121
by utilizing differential scanning calorimetry to test the polyarylsulfone shown in the formula (I-a) obtained in the example 1, a DSC secondary temperature rise curve chart is obtained, as shown in figure 1, figure 1 is a DSC secondary temperature rise curve chart of the polyarylsulfone shown in the formula (I-a) obtained in the example 1 of the invention, and as can be seen from figure 1, the Tg is 365 ℃, which indicates that the polyarylsulfone has higher heat-resistant temperature.
A thermogravimetric analyzer is used for testing the polyarylsulfone shown in the formula (I-a) obtained in the example 1 to obtain a thermogravimetric analysis diagram, as shown in fig. 2, and fig. 2 is a thermogravimetric analysis diagram of the polyarylsulfone shown in the formula (I-a) prepared in the example 1 of the invention; as can be seen from FIG. 2, the 5% thermal weight loss temperature is as high as 470 ℃, and the 800 ℃ carbon residue ratio is 42.0%, which shows that the polyarylsulfone has good thermal decomposition performance and high ablation resistance.
The obtained polyarylsulfone shown in the formula (I-a) is subjected to a dissolution performance test, and the test method comprises the steps of accurately weighing 5mg of a sample to be tested, and dissolving the sample in 1mL of solvent. + represents complete dissolution; + heat soluble, + -swellable, -completely insoluble. Solvent abbreviation: DMF is N, N-dimethylformamide; DMAc is N, N-dimethylacetamide; NMP is N-methylpyrrolidone; THF was tetrahydrofuran, and the results are shown in Table 1, Table 1 being the results of the solubility tests for the polyarylsulfones prepared in the examples and comparative examples.
TABLE 1
Figure BDA0000984912890000131
Example 2
Sequentially adding 1.482g (0.01mol) of 5-methylbenzimidazole ketone (mHBI), 2.543g (0.01mol) of difluorodiphenyl sulfone (DFS), 1.590g of potassium carbonate, 12.5g N-Cyclohexylpyrrolidone (CHP) and 15ml of toluene into a 100ml three-neck round-bottom flask, heating to 150 ℃, keeping the temperature for 2h, removing water by azeotropy, heating to remove the toluene, continuing to heat to 190 ℃, reacting for 4.5h, heating to 205 ℃, reacting for 2h, cooling, adding 10ml of dimethylacetamide for dilution, precipitating in a mixed solution of ethanol, water and hydrochloric acid, filtering precipitates, extracting with deionized water in a Soxhlet extractor for 15h, removing inorganic salts and a reaction solvent, drying to obtain the polyarylsulfone shown in the formula (I-b),
the reaction formula is as follows:
Figure BDA0000984912890000132
the polyarylsulfone represented by the formula (I-b) obtained in example 2 was subjected to a glass transition temperature test to give a Tg of 325 ℃.
The obtained polyarylsulfone shown in the formula (I-b) is subjected to a dissolution performance test, and the test method comprises the steps of accurately weighing 5mg of a sample to be tested, and dissolving the sample in 1mL of solvent. + represents complete dissolution; + heat soluble, + -swellable, -completely insoluble. Solvent abbreviation: DMF is N, N-dimethylformamide; DMAc is N, N-dimethylacetamide; NMP is N-methylpyrrolidone; THF was tetrahydrofuran, and the results are shown in Table 1, Table 1 being the results of the solubility tests for the polyarylsulfones prepared in the examples and comparative examples.
Example 3
Adding 0.811g of 5, 6-dimethyl benzimidazolone (DmHBI), 0.672g of benzimidazolone (HBI), 2.543g of difluoro diphenyl sulfone (DFS), 2.763g of potassium carbonate, 0.500g of calcium carbonate, 22g of sulfolane and 18ml of toluene into a 100ml three-neck round-bottom flask in sequence, heating to 130 ℃, preserving heat for 2 hours, removing water by azeotropy, heating to remove toluene, continuing heating to 200 ℃, reacting for 3.5 hours, cooling, adding 20ml of dimethyl acetamide for dilution, precipitating in a mixed solution of ethanol, water and acetic acid, filtering precipitates, extracting with deionized water for 12 hours in a Soxhlet extractor, removing inorganic salts and a reaction solvent, and drying to obtain the polyarylsulfone copolymer shown in formula (II-a), wherein the reaction formula is as follows:
Figure BDA0000984912890000141
the polyarylsulfone represented by the formula (II-a) obtained in example 3 was subjected to a glass transition temperature test to obtain a Tg of 360 ℃.
The obtained polyarylsulfone shown in the formula (II-a) is subjected to a dissolution performance test, and the test method comprises the steps of accurately weighing 5mg of a sample to be tested, and dissolving the sample in 1mL of solvent. + represents complete dissolution; + heat soluble, + -swellable, -completely insoluble. Solvent abbreviation: DMF is N, N-dimethylformamide; DMAc is N, N-dimethylacetamide; NMP is N-methylpyrrolidone; THF was tetrahydrofuran, and the results are shown in Table 1, Table 1 being the results of the solubility tests for the polyarylsulfones prepared in the examples and comparative examples.
Example 4
Sequentially adding 1.184g of 4, 5-diphenyl imidazolone, 0.550g of hydroquinone, 2.543g of difluoro diphenyl sulfone (DFS), 2.763g of potassium carbonate, 1.500g of calcium carbonate, 25g of sulfolane and 18ml of toluene into a 100ml three-neck round-bottom flask, heating to 130 ℃, preserving heat for 2 hours, removing water by azeotropy, heating to remove toluene, continuously heating to 185 ℃, reacting for 7 hours, cooling, adding 20g of sulfolane for dilution, precipitating in a mixed solution of ethanol, water and hydrochloric acid, filtering precipitates, extracting with deionized water for 24 hours in a Soxhlet extractor, removing inorganic salts and a reaction solvent, drying to obtain the polyarylether sulfone copolymer shown in the formula (II-b),
the reaction formula is as follows:
Figure BDA0000984912890000151
the polyarylsulfone represented by the formula (II-b) obtained in example 4 was subjected to a glass transition temperature test to give a Tg of 235 ℃.
The obtained polyarylsulfone shown in the formula (II-b) is subjected to a dissolution performance test, and the result shows that the test method comprises the step of accurately weighing 5mg of a sample to be tested and dissolving the sample in 1mL of solvent. + represents complete dissolution; + heat soluble, + -swellable, -completely insoluble. Solvent abbreviation: DMF is N, N-dimethylformamide; DMAc is N, N-dimethylacetamide; NMP is N-methylpyrrolidone; THF was tetrahydrofuran, and the results are shown in Table 1, Table 1 being the results of the solubility tests for the polyarylsulfones prepared in the examples and comparative examples.
Example 5
Adding 1.502g of 2-Mercaptobenzimidazole (MBI), 2.543g of difluoro diphenyl sulfone (DFS), 2.763g of potassium carbonate, 1.500g of calcium carbonate, 25g of sulfolane and 12ml of toluene into a 100ml three-neck round-bottom flask in sequence, heating to 130 ℃, keeping the temperature for 2h, removing water by azeotropy, heating to remove the toluene, continuing heating to 175 ℃, reacting for 3h, cooling, adding 20ml of dimethylacetamide for dilution, precipitating in a mixed solution of ethanol, water and acetic acid, filtering the precipitate, extracting with deionized water in a Soxhlet extractor for 12h, removing inorganic salts and a reaction solvent, and drying to obtain the polyarylsulfone shown in formula (I-c), wherein the reaction formula is as follows:
Figure BDA0000984912890000161
the polyarylsulfone represented by the formula (I-c) obtained in example 5 was subjected to a glass transition temperature test to obtain a Tg of 205 ℃.
The obtained polyarylsulfone shown in the formula (I-c) is subjected to a dissolution performance test, and the test method comprises the steps of accurately weighing 5mg of a sample to be tested, and dissolving the sample in 1mL of solvent. + represents complete dissolution; + heat soluble, + -swellable, -completely insoluble. Solvent abbreviation: DMF is N, N-dimethylformamide; DMAc is N, N-dimethylacetamide; NMP is N-methylpyrrolidone; THF was tetrahydrofuran, and the results are shown in Table 1, Table 1 being the results of the solubility tests for the polyarylsulfones prepared in the examples and comparative examples.
Example 6
Adding 0.896g of 5-nitrobenzimidazole ketone (nHBI), 1.256g of dichlorodiphenyl sulfone (DCS), 1.000g of potassium carbonate, 0.550g of calcium carbonate, 10ml of sulfolane and 12ml of toluene into a 100ml three-neck round-bottom flask in sequence, heating to 130 ℃, preserving heat for 2h, removing water by azeotropy, heating to remove toluene, continuously heating to 185 ℃, reacting for 7h, cooling, adding 12ml of dimethylacetamide for dilution, precipitating in a mixed solution of ethanol, water and acetic acid, filtering precipitates, extracting with deionized water in a Soxhlet extractor for 12h, removing inorganic salts and a reaction solvent, and drying to obtain the polyarylsulfone shown in formula (I-d), wherein the reaction formula is as follows:
Figure BDA0000984912890000162
the polyarylsulfone represented by the formula (I-d) obtained in example 6 was subjected to a glass transition temperature test to give a Tg of 322 ℃.
The obtained polyarylsulfone shown in the formula (I-d) is subjected to a dissolution performance test, and the test method comprises the steps of accurately weighing 5mg of a sample to be tested, and dissolving the sample in 1mL of solvent. + represents complete dissolution; + heat soluble, + -swellable, -completely insoluble. Solvent abbreviation: DMF is N, N-dimethylformamide; DMAc is N, N-dimethylacetamide; NMP is N-methylpyrrolidone; THF was tetrahydrofuran, and the results are shown in Table 1, Table 1 being the results of the solubility tests for the polyarylsulfones prepared in the examples and comparative examples.
Example 7
Adding 0.746g of 5-aminobenzimidazole ketone (aHBI), 2.543g of difluoro diphenyl sulfone (DFS), 1.592g of phenolphthalein, 1.590g of potassium carbonate, 12.5g N-cyclohexyl pyrrolidone and 12ml of toluene in sequence into a 100ml three-neck round-bottom flask, heating to 150 ℃, preserving heat for 2h, removing water by azeotropy, heating to 190 ℃, reacting for 4.5h, heating to 205 ℃, reacting for 2h, cooling, adding 10ml of N-cyclohexyl pyrrolidone for dilution, precipitating in a mixed solution of ethanol, water and acetic acid, filtering precipitates, extracting with deionized water for 12h in a Soxhlet extractor, removing inorganic salts and reaction solvents, and drying to obtain the polyarylether sulfone copolymer shown in formula (II-c), wherein the reaction formula is as follows:
Figure BDA0000984912890000171
the polyarylsulfone represented by the formula (II-c) obtained in example 7 was subjected to a glass transition temperature test to give a Tg of 320 ℃.
The obtained polyarylsulfone shown in the formula (II-c) is subjected to a dissolution performance test, and the test method comprises the steps of accurately weighing 5mg of a sample to be tested, and dissolving the sample in 1mL of solvent. + represents complete dissolution; + heat soluble, + -swellable, -completely insoluble. Solvent abbreviation: DMF is N, N-dimethylformamide; DMAc is N, N-dimethylacetamide; NMP is N-methylpyrrolidone; THF was tetrahydrofuran, and the results are shown in Table 1, Table 1 being the results of the solubility tests for the polyarylsulfones prepared in the examples and comparative examples.
Comparative example 1
Adding 0.276g of benzimidazolone (HBI), 0.51g of difluorodiphenyl sulfone (DFS), 0.28g of potassium carbonate, 0.20g of calcium carbonate, 1.6g of sulfolane and 3ml of water-carrying agent 1-chlorobenzene into a 25ml three-neck round-bottom flask in sequence, heating to 130 ℃, preserving heat for 2 hours, removing water by azeotropic distillation, heating to remove 1-chlorobenzene, continuing heating to 200 ℃, reacting for 2 hours, adding 2g of sulfolane, preserving heat for 2.5 hours at 200 ℃, cooling, diluting in dichloromethane, pouring into 100ml of a mixed solution of methanol and acetic acid (v/v:100:1) for precipitation, filtering the precipitate, extracting with deionized water in a Soxhlet extractor for 12 hours, removing inorganic salts and a reaction solvent, and drying to obtain the polymer with the structural formula shown as I-c:
Figure BDA0000984912890000181
the polyarylsulfone obtained in example 8 was subjected to a glass transition temperature test to give a Tg of 348 ℃.
The obtained polyarylsulfone shown in the formula (I-c) is subjected to a dissolution performance test, and the test method comprises the steps of accurately weighing 5mg of a sample to be tested, and dissolving the sample in 1mL of solvent. + represents complete dissolution; + heat soluble, + -swellable, -completely insoluble. Solvent abbreviation: DMF is N, N-dimethylformamide; DMAc is N, N-dimethylacetamide; NMP is N-methylpyrrolidone; THF was tetrahydrofuran, and the results are shown in Table 1, Table 1 being the results of the solubility tests for the polyarylsulfones prepared in the examples and comparative examples.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.

Claims (1)

1. A polyarylsulfone is characterized in that the polyarylsulfone has a structure shown in a formula (I-a), a formula (I-b), a formula (I-c), a formula (I-d), a formula (II-a), a formula (II-b) or a formula (II-c),
Figure FDF0000007331660000011
wherein n is an integer not less than 2, and m is an integer not less than 2.
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